Method of printing synthetic linear polyester sheet materials

ABSTRACT

A method is provided for printing synthetic linear polyester sheet materials such as films and fabrics, in which the area of material which is to be printed is initially treated with a halogenated aromatic hydrocarbon at an elevated temperature. The halogenated aromatic hydrocarbon is then removed and a composition containing a dyestuff is applied to the treated area to provided desired indicia on the polyester material. The method of this invention is particularly useful in providing printed polyester films and printed heavy weight fabrics such as carpeting.

United States Patent McCullough et a1.

[ Feb. 22, 1972 [54] METHOD OF PRINTING SYNTHETIC LINEAR POLYESTER SHEET MATERIALS [72] Inventors: Robert W. McCullough, Riverside, Conn.;

Vernon C. Smith, Huntersville; Frederick E. Barwick, III, Charlotte; James B. l-Iobgood, Roxboro, all of NC.

.[73] Assignee: Collins 8: Aikman Corporation, New

York, NY.

[22] Filed: Sept. 15, 1969 [21] App1.No.: 857,843

[52] U.S.Cl ..8/4, 8/174, 8/175, 8/94 [51] Int. Cl. ..D06p 3/00 [58] Field of Search ..8/4, 62, 175, 174, 94

[56] References Cited UNITED STATES PATENTS 2,999,002 9/ 1 961 Dayvault .8/94

Nusslein .,8/114.6

Primary ExaminerD0nald Levy Assistant ExaminerB. Bettis AttorneyPaul & Paul ABSTRACT A method is provided for printing synthetic linear polyester sheet materials such as films and fabrics, in which the area of material which is to be printed is initially treated with a halogenated aromatic hydrocarbon atan elevated temperature. The halogenated aromatic hydrocarbon is then removed and a composition containing a dyestuff is applied to the treated area to provided desired indicia on the polyester material. The method of this invention is particularly useful in providing printed polyester films and printed heavy weight fabrics such as carpeting.

10 Claims, 6 Drawing Figures PATENTEUFEBZZ m2 3, 644, 080

VENTORS ROBERT W. M CULLOUGH VERN C. ITH F RE CK ARWICKJII K BY Wv M ATTORNEYS.

METHOD OF PRINTING SYNTHETIC LINEAR POLYESTER SHEET MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention is concerned with a method for printing synthetic linear polyester sheet materials.

2. Description of the Prior Art Synthetic linear polyesters, for example, polyethylene terephthalate, have excellent physical properties which make them useful in many different types of applications. The polyesters exhibit a high tensile strength, are water resistance, and have a high modulus of elasticity, and other desirable properties. The polyesters are produced in various forms such as films and fibers. The films are used in applications wherein high strength is required, such as packaging and the like. The polyester fibers are used to make fabrics of various types from relatively light weight materials, such as dress goods, to very heavy weight fabrics, such as carpeting.

One of the major problems encountered with the polyester films and fibers is their relatively poor dyeability. Polyesters have little natural affinity for dyestuffs. In order to dye polyester fabrics and films in solid shades the dyestuffs are usually applied along with a relatively large amount of a carrier compound. However, even using a carrier long dyeing times are required in order to exhaust the dyebath. With medium to heavy shades, it is not uncommon to require 60 minutes or more to exhaust the dyestuff from the bath.

Heretofore, it has been virtually impossible to obtain satisfactory prints on polyester fabrics and films. Because of the long dyeing cycles which are required it is not feasible to use the carrier dyeing method in printing. This is especially true in films since the cost competition in the packaging art made it economically impractical to use long and expensive dyeing techniques.

It has been suggested to print resin-bonded pigments on the films and fabrics. This is not a satisfactory solution. Printing with resin bonded pigments is expensive and the results are best at only marginal. Polyesters do not form strong bonds with the resins and accordingly the prints are relatively easy to remove. The poor adhesion of the prints presented special problems in the packaging art since if the printed indicia was removed, or even damaged, it distracted from the overall appearance of the final package.

In the textile art the inability to obtain satisfactory prints with polyesters has to some extent limited to the use of polyesters in certain areas. This is particularly true in the carpeting field. Polyester fibers have excellent properties for use in carpeting. However, the polyesters have heretofore been restricted to uses in carpeting wherein the yarn could be dyed prior to tufting or weaving or dyed a solid shade in the piece goods. A large and growing portion of the carpet market is in the printed carpeting field. Since the polyesters have heretofore not been printable the polyesters have been excluded from this market.

It is an object of this invention to provide a method for printing synthetic linear polyester sheet materials.

It is a further object of this invention to provide a method which is simple, inexpensive and in which the printing has improved fastness to the polyester sheet material.

Other objects and advantages of this invention will become further apparent from a further reading of the specification and subjoined claims.

SUMMARY OF THE INVENTION The objects of this invention have been achieved by contacting the polyester sheet material to be printed in predetermined sections with a halogenated aromatic hydrocarbon at an elevated temperature; removing the aromatic halogenated hydrocarbon to provide areas having improved dyeability and thereafter forming a desired indicia on the polyester material by applying a composition containing a dyestuff to at least a portion ofthe treated area.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic illustration of one method which may be employed to improve the dyeability of polyester sheet materials.

FIG. 2 is a schematic illustration of apparatus for printing of polyester sheet materials.

FIG. 3 is a schematic illustration of an alternate embodiment of apparatus for printing polyester sheet materials.

FIG. 4 is a top plane view of the polyester sheet materials taken as indicated by the lines and arrows 4-4 of FIG. 2.

FIG. 5 is a top plane view of the polyester sheet materials taken as indicated by the lines and arrows 5-5 of FIG. 3.

FIG. 6 is a top plane view of the polyester sheet materials taken as indicated by the lines and arrows 66 of FIGS. 2 and 3.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The synthetic linear polyesters which are preferably treated in accordance with the present invention are the condensation polymerization products of dicarboxylic acids and polyhydric alcohols. The repeating structural units of the polymer chain include at least one divalent carbocylic ring containing at least six carbon atoms which is present as an integral part of the polymer chain and have a minimum of four carbon atoms between the points of attachment of the ring in the polymer chain. The preferred synthetic linear polyesters are of the polyethylene terephthalate type. Other types of polyesters are likewise employable such as those obtained by polymerizing a dicarboxylic acid such as terephthalic acid, bromoterephthalic acid, 4, 4-benzophenonedi-carboxylic acid and so forth with glycols such as those of the formula HO(CH ),,OI-I wherein, n is a whole number from two to 10, diethylene glycol, neopentylene glycol and the like. The commercially available polyester materials of the above described type are commercially known by the trade names Dacron, Kodel II and Kodel 241, Mylar and Encron.

When referring to synthetic linear polyester sheet materials in this specification, it is intended to include both polyesters which are formed into continuous films and also fabrics which are made from polyester fibers. The polyester films which are treated in accordance with the present invention are preferably formed in thicknesses from 0.5 mils to about 20 mils in thickness. The textile fabrics which are printed in accordance with the present invention may be of various structures and weights. The fabrics may be woven, knitted or of a nonwoven construction. The fabrics may also be a composite type fabric. Of this type of fabric particular attention is directed to the tufted fabrics which can have, for example, a cotton or jute backing and a polyester yarn face. The weight of the goods treated can be from a fraction of an ounce per square yard, such as dress goods or tricot fabrics to relatively heavy weight goods such as tufted carpeting.

The textile fabrics treated in accordance with this invention are preferably comprised of percent polyester fibers but it is also possible to treat blends such as cotton-polyester blends in accordance with the present invention.

' The halogenated aromatic hydrocarbons which are employed in the present invention may be monocyclic or bicyclic hydrocarbons with the monocyclic hydrocarbons being preferred. The halogenated aromatic hydrocarbons are represented by the formula R2 wherein R and R are the same or different and represent hydrogen, an alkyl having one to four carbon atoms such as methyl, ethyl, n-propyl, isopropyl, and n-butyl or an alkenyl having two to four carbon atoms such as vinyl, l-propenyl and Z-butenyl. When R and R are attached to vicinal carbon atoms they may be attached to each other to form a five to six membered aliphatic or aromatic ring when taken together with the vicinal carbon atoms of the aromatic ring of the compound of formula I, with the naphthalene ring system being the preferred ring systems when R and R are joined together. R is a lower alkylene having one to four carbon atoms such as methylene, ethylene, propylene and butylene, stands for a halogen such as fluorine, chlorine, bromine or iodine, n is a whole number from one to three and when n is two or more X can stand for the same or different halogens.

The polyester sheet material may be treated with the halogenated aromatic hydrocarbon in either the liquid phase or the vapor phase as will be explained in greater detail below.

The halogenated aromatic hydrocarbon employed in the liquid phase method of the present invention should have a melting point below 120 C. and be a liquid at the desired treating temperature. The ideal compound for employment in the liquid phase method should melt at a temperature below 130 C. and have a boiling point above 160 C. and more preferably above 200 C. The halogenated aromatic hydrocarbon should be substantially anhydrous. However, it can contain minor amounts of water and will tend to pick up small amounts of water from the polyester being treated. Since the treatment is conducted at elevated temperatures, the water is volatilized and removed from the treating bath.

The preferred halogenated aromatic hydrocarbons for employment in liquid phase method are represented by the formula wherein X is chlorine or bromine and n is two and more preferably three.

The mono-halogenated compounds wherein R and R are hydrogen, that is, the mono-halo-benzenes, are generally not employed in liquid phase method of this invention because of their relatively low boiling points. However, the monohalogenated benzenes can be employed if the process is conducted at a temperature below their boiling point or if the process is conducted under pressure conditions. Even if the process is conducted at normal pressures, compounds such as bromobenzene and iodobenzene can be employed to some advantage.

The dihalogenated benzenes are quite useful in the liquid phase method of the present invention and are one of the preferred class of compounds. All of the isomers of the dihalogenated benzenes such as the dichloro, the dibromo and the diiodo benzenes give excellent results. The mixed dihalogenated compounds, such as, mand pbromochlorobenzenes and the iodobromobenzene compounds, such as the ortho and meta isomers are likewise useful.

The most important class of compounds for employment in the liquid phase of the present invention are the trihalogenated benzenes. All of the isomers of the trichloro benzenes, such as the 1, 2, 3-trichloro, l, 2, 4-trichloro and the l, 2, S-trichloro benzenes are the most preferred compounds for employment in the present invention. The other trihalogenated benzenes, such as the trifluoro, the tribromo and the triiodo and the various mixed halogen compounds are likewise useful and are in the preferred class compounds.

Of the compounds wherein R and R represent alkyls having one to four carbon atoms, by far the most important class of compounds are the halogenated toluenes and halogenated xylenes compounds. With even the monohalogenated compounds, such compound as the chlorotoluenes and bromoxylene's, are quite suitable for use in the liquid phase method.

Of the compounds wherein R, and R are attached to each other to form a five to six-membered ring, particular attention is directed to the halogenated compounds of the naphthalene series such as the monohalogenated naphthalene such as lbromo-5 2-bromo-, and l-chloro-naphthalenes and the dihalogenated naphthalenes such as l, Z-dichloro, l, 3- dichloro and l, 4-dichloro naphthalenes.

Of the compounds were R is a lower alkylene and m is two particular attention is directed to compounds such as a chlorotoluene, ao-dichloro-toluene, a bromotoluene and abromo-o-xylene.

The same type of compounds that are employed in the liquid phase method can likewise be employed in the vapor phase method. it is, however, of considerable advantage to use compounds which have a lower boiling point. In this regard it should be noted that the compound of the general formula wherein X is a halogen such as fluorine, chlorine, bromine or iodine and n" is a whole number from one and two are the preferred compounds. Of this class of compounds the most important compounds are the monohalogenated benzene such as chloroand bromo-benzene and the dihalogenated benzenes such as dichloro-dibromo and chloro-bromobenzene.

It has been found that when polyester sheet materials such as the fabric and films of the type described above are initially treated with the halogenated aromatic hydrocarbon at an elevated temperature and then the halogenated aromatic hydrocarbon is removed from the polyester material, that the treated area can readily be printed using conventional printing method. The prints that are obtained are characterized by being true dyeing, that is, the dyestuff is penetrated into the structure of the fibers and films.

The halogenated aromatic hydrocarbons can be applied to the polyesters by immersing the polyester in a bath of the halogenated aromatic hydrocarbon. The bath should be heated to a temperature of between about C. and 200 C. with temperatures of to C. being most preferred. The immersion time should be limited to 10 to about 20 seconds. The exact temperatures and times which are optimum for each type of fabric and film is dependent upon a number of factors. The most important factors are the particu' lar halogenated aromatic hydrocarbon that is employed and the weight per square yard of the polyester sheet materials that are being treated. The boiling point of the particular halogenated aromatic hydrocarbon is the limiting factor on the upper temperature which can be employed in the liquid phase method. Heavy weight goods should be treated at higher temperatures or for longer periods of time than that required for the treatment of relatively thin polyester sheet materials in order to obtain an equivalent treatment. The time of 10 seconds is about the shortest time which can be employed and still obtain satisfactory results. It should be noted that shorter treatment times can be employed and that these will to some extent improve the dyeability of the polyester fibers. Treatment times in excess of 20 seconds do not have any particular advantage since the excess time over 20 seconds does not cause any significant improvement in the printability of the polyester films and fabrics.

As noted above the halogenated aromatic hydrocarbons can be applied to the polyester sheet material in the vapor phase. The advantage of this method is that the vapors tend to penetrate the polyester fabrics and films at a faster rate than the liquid materials and higher treatment temperatures can more readily be obtained. The lower temperature limit for the vapor treatment is the boiling point of the halogenated aromatic hydrocarbon employed. In the case of one of the preferred compounds for employment in the present invention, namely monochloro-benzene, the lower limit is 132 C. The upper temperature limit in the vapor phase method is that temperature wherein the vapors tend to heat the polyester sheet material being treated above their shrink or decomposition temperatures. The most preferred method of conducting the vapor phase treatment is to control the relative temperature of the halogenated aromatic hydrocarbon vapor and the polyester sheet material to be treated in a ratio such that the vapors will tend to condense in a thin film on the polyester material during treatment. The time limit for treatment in the vapor phase is about the same as that employed in the liquid method, that is, to seconds. In general, however, shorter treatment times are more preferred used with the vapor phase method than with the liquid phase method.

After treating the polyester sheet material the halogenated aromatic hydrocarbon is removed from the polyester. Various types of extraction methods can be employed for this step. One of the preferred methods is to pass the treated material through a series of rinse baths of a solvent with which the halogenated aromatic hydrocarbon is miscible until all or substantially all of the treating agent is removed. The extraction solvent is then removed by conventional means such as passing the extracted polyester sheet material over a set of can dryers. Extraction solvents which have proven to be most useful are the aliphatic halogenated hydrocarbons such as methylene chloride, trichloroethylene, l, 'l, ltrichloro ethane, perchloroethylene and mixtures thereof.

The halogenated aromatic hydrocarbons treating media can also be removed by passing the treated material into a vacuum chamber which causes the treating media to volatilize.

In a commercial practice substantially all of the aromatic halogenated hydrocarbons and the extraction solvents are recovered and purified for reuse in the process which substantially reduces the total cost of the process.

The treated areas of the polyester sheet material have substantially improved dyeability. These areas can be printed with compositions containing conventional dyestuffs used for the polyester material, such as the dispersed dyestuffs including dyestuffs in the azo, azomethine, nitroarene and anthraquinone chemical classes. The dyeing can be conducted in a relatively short time without the requirement of the use of a carrier or other expedients to force the dyestuff onto the polyester fibers or films. The treatment areas can readily be dyed using printing methods, such as the pad steam and the like. The dyestuffs are rapidly fixed onto the polyester fabrics and films. This is not possible with the use of the untreated polyester fibers and films. The resulting prints on the polyester sheet material are characterized by having the dyes penetrated into the polyester structure rather than being simply adhered to the surface of the material as was common in the prior art methods. Particularly good results are obtained on films in that the printed area can be printed so as to remain transparent even though dyed. This type of film is extremely useful in the packaging art since the desired indicia can be printed onto the film without hiding the contents of the package.

In order to further illustrate the methods of the present invention, reference is made to the drawings. In FIG. 1 the treatment of an entire sheet of a polyester material is schematically shown. In the illustrated process a continuous strip of material 10 which may be either a film or fabric is immersed in a bath 12 of a halogenated aromatic hydrocarbon for the times and at the temperatures noted above. The entire width of the strip 10 is treated with the halogenated aromatic hydrocarbon treating agent. The treating agent is then extracted from the polyester sheet material in a bath 14 of a solvent with which the treating agent is miscible. As illustrated a single bath is shown. However, in practice a series of extraction baths would be used. The extraction solvent is then removed by passing the treated polyester through a dryer 16. The entire area of the final product 18 has improved dyeability. This material can now be printed in the conventional manner with the desired indicia. This method of treatment is particularly useful when large areas of the polyester sheet material are to be printed or when several different colors are to be applied to the treated material.

An alternate method is shown in FIG. 2 which is especially useful for manufacturing printed films. The polyester sheet material 20 is padded with a thickened halogenated aromatic hydrocarbon composition 22. To prepare the thickened composition materials such as soaps, silica thickeners and special carboxymethyl cellulose derivatives can be used as the thickeners. The thickened compositions 22 are printed onto the polyester sheet material with an engraved roll 24 having the desired indicia. The printed sheet 22 is then advantageously fed under a heated roll 28 and/or under a series of heat lamps 30 which supply sufficient heat to the printed sheet 26 to cause the halogenated aromatic hydrocarbon printed onto the sheet to penetrate through the sheet. If the residual thickening agents are removed at this point the printed sheet 24 would appear to be unchanged. However, it would have visibly indistinguishable areas 32 which have improved dyeability wherein the halogenated aromatic hydrocarbon was printed onto the material 24.

The halogenated aromatic hydrocarbon is removed in a vacuum chamber 34. It could, of course, also be removed in a series of extraction baths as is shown in the method illustrated in FIG. 1.

The treated material 36 is fed into a continuous dyeing apparatus 38 and dyed with a formulation which contains the dyestuffs and other usual additives but does not contain any carrier. Since the polyester which is untreated has little natural affinity for the dyestuff in the untreated form, the untreated area 40 does not dye, but the treated area 32 readily accepts the dyestuff. The dyed material is then removed and passed through a dryer 42. The final product has treated areas 32 which are dyed the desired shade and untreated areas 40 which are undyed.

An alternate method of obtaining sharp prints on polyester sheet materials is shown in FIG. 3. A polyester sheet material 46 is printed with a printing apparatus 48 with a resist agent 50 which is insoluble in the halogenated aromatic hydrocarbon under the treating conditions which will be employed. One of the most inexpensive but highly effective materials for the purpose is starch. The resist agent is dried in an oven 52. The polyester sheet material at this point has a resist coated area 56 and an exposed untreated area 58. This material is then advanced through a vapor chamber 56 and treated with a vapor of the halogenated aromatic hydrocarbon. The halogenated aromatic hydrocarbon is then removed from the treated material in the vapor chamber 58. The exposed area 58 of the treated material are now readily dyeable. The polyester material is dyed in a dyebath which contains the dyestuff but no carrier. The resist is removed leaving undyed areas 44 and dyed areas 32.

The method described above were illustrated in a continuous manner. However, it should be appreciated that the process can be conducted in a noncontinuous manner. In addition, the equipment can be varied, such as the extraction means and still be within the scope of the present invention. Furthermore, the dyestuff can be printed onto treated material in the method illustrated in FIG. 2 and 3 rather than being applied from an aquous dyebath.

In order to further illustrate this invention, reference is made to the following examples. These examples are given here for the purposes of illustrating the present invention and are not intended to limit the scope of the subjoined claims. All percentages are percents by weight, not percents by volume unless otherwise noted.

EXAMPLE 1 A 4 ounce square fabric made of spun polyethylene terephthalate fiber, commercially known as Dacron, was immersed in l, 2, 4- trichlorobenzene which had been heated to 120 C. for 10 seconds. The l, 2, 4- trichlorobenzene was removed in a series of three extractionsv with l, l, ltrichloroethane and the fabric was dried at C. for 30 seconds to remove the residual I l, ltrichloroethane. After drying, the fabric was then screen-printed with the design CA with a printing paste of the following composition:

1.5 g./l. wetting agent (Barasol BRM) 1.5 g./l. ammonium sulfate 1.5 g./l. locust bean extract (Polygum 260) 4 g./l. thiodiglycol 1.5 g./l. Cl Disperse Blue 27 After applying the printing paste, the fabric was steamed at 100 C. for 6 minutes. The fabric was scoured in water at 30 C. Complete fixation of the dyestuff on the fabric was obtained.

EXAMPLE 2 A sample of fabric as described in Example 1 but which had not been treated with 1, 2, 4- trichlorobenzene was printed with the printing paste as previously described. After steaming at 100 C. for 6 minutes and a scour in water at 30 C., almost no fixation of the dyestuff occurred.

EXAMPLE 3 A 4 ounce 80 square fabric made of spun polyethylene terephthalate fiber, commercially known as Dacron, was screen-printed with the design CA with a printing paste of the following composition:

92 percent 1, 2, 4- trichlorobenzene 8 percent Thixin-R (A thixotropic agent for solvents) The fabric was then heated at 120 C. for 10 seconds. The l, 2, 4- trichlorobenzene was removed in a series of three extractions with 1, 1, ltrichloro-ethane and the fabric was dried at 90 C. for 30 seconds to remove the residual l, l, 1- trichloroethane. The fabric was unchanged in physical appearance after drying.

The printed fabric was dyed at 99-100 C. for one-quarter hour in 30:1 liquor ratio dyebath containing 1.0 percent OWF Cl Disperse Red 60 0.5 percent OWF Sodium acetate After dyeing the fabric was washed to remove any excess dyestuff. The design CA which had previously been printed with 1, 2, 4- trichlorobenzene on the fabric was a bright red shade. Areas adjacent to the print were stained a pale pinkish shade.

EXAMPLE 4 A 4 ounce 80 square fabric made of spun polyethylene terephthalate fiber, commercially known as Dacron was printed with an engraved roller designed such that the design CA was not covered with the following composition:

10 percent Corn starch 2 percent thickener (Polygum 260) 88 percent water The fabric was dried at 100 C. until it was essentially free of water. After drying the fiber was allowed to pass into a chamber which was saturated with vapors of 1, 2- dichlorobenzene at 180 C. for a period of 10 seconds. The 1, 2- dichlorobenzene was removed in a series of three extractions with 1, l, 1- trichloroethane and the fabric was dried at 90 C. for 30 seconds to remove the residual l, 1, ltricbloroethane.

The treated fabric was dyed at 99-l00 C. for one-quarter hour in 30:1 liquor ratio dyebath containing 1.0 percent OWF Cl Disperse Red 65 0.5 percent OWF Sodium Acetate After dyeing the fabric was washed to remove any excess dyestuff. The design CA was a full shade of red whereas the areas adjacent to it were stained a light shade of red.

EXAMPLE Fabric samples of 4 ounce 80 square fabric made of spun polyethylene terephthalate fiber, commercially known as Dacron, were printed with 1, 2, 4- trichlorobenzene thickened with Thixin-R as described in Example 3. The samples were heated at various temperatures and for varying periods of time, rinsed with three portions of 1, 1, 1- trichloroethane to remove the 1, 2, 4- trichlorobenzene and dried at 90 C. for 30 seconds to remove the residual 1, l, 1- trichloroethane. The samples were dyed at 99100 C. for one-quarter hour in 30:1 liquor ratio dyebath containing 1.0 percent OWF C1 Disperse Blue 27 0.5 percent OWF Sodium Acetate After dyeing the samples were washed to remove any excess dyestuff. The shades of the dyeing were as follows:

Sample Temperature Time Depth of Shade 1 120 C. 10" seconds Full blue shade 2 120 C. 1 second As above 3 120 C. 5 seconds As above 4 120 C. 10 seconds As above 5 120 C. 20 seconds As above 6 140 C. I second As above 7 160 C. 10 seconds As above 8 160 C. 1 second As above 9 160 C. 5 seconds Full blue shade, Slight shrinkage 1O 160 C. 10 Seconds As above 1 1 160 C. 20 seconds Full blue shade,

Shrinkage EXAMPLE 6 Samples of 2 mil polyethylene terephthalate film, commercially known as Mylar, were printed with l, 2, 4- trichlorobenzene thickened with Thixin-R as described in Example 3. The samples were heated at various temperatures and for varying periods of time, rinsed with several portions of 1, 1, ltrichloroethane to remove the 1, 2, 4- trichlorobenzene and dried at C. for 30 seconds to remove the residual 1, 1, 1- trichloroethane. The samples were dyed at 99l00bL C. for one-quarter hour in 30:] liquor ratio dyebath containing 1.0 percent OWF Disperse Yellow 54 0.5 percent OWF Sodium Acetate After dyeing the samples were washed to remove any excess dyestuff. The shades of the dyeing were as follows:

A tufted carpet sample made Encron brand polyethylene terephthalate fiber was immersed in a bath of 1, 2, 4- trichlorobenzene heated to C. for a period of 12 seconds and then rinsed in three separate portions of 1, 1, 1- trichloroethane. Subsequently, the carpet was dried at 90 C. for 30 seconds to remove the residual rinse liquid. The carpet was then screen-printed with a printing paste as described in Example 1. After applying the printing paste, the carpet was steamed at 100 C. for 6 minutes. Complete fixation of the dyestuff on the carpet was obtained as evidenced by the clear rinse liquid obtained from a water wash after steaming.

EXAMPLE 8 A tufted carpet sample as described in Example 7 which had not been treated with 1, 2, 4- trichlorobenzene was screenprinted with the printing paste as described in Example 1 and after subsequent steaming showed almost no fixation of dyestuff.

EXAMPLE 7 The procedure described in Example 6 was repeated with the sample being treated at C. with various other halogenated aromatic hydrocarbons as noted below.

EXAMPLE l0 The procedure described in Example I was repeated with the sample being treated at l30 C. with 1,2,4- trichlorobenzene and subsequently rinsed with various other 1,2,4-trichlorobenzene miscible solvents as noted above.

EXAMPLE 11 A 2.0 mil film made of polyethylene terephthalate, commercially known as Mylar, was screen-printed as described in Example 4. The film was dried at 100 C. and subsequently passed into a chamber which was saturated with vapors of chlorobenzene at l32 C. for a period of seconds. The treated film was flash-dried by passing through an evacuated chamber maintained at 100 C. in order to remove the chlorobenzene.

The treated film was dyed at 99-100 C. for one-quarter hour in 30:1 liquor ratio dyebath containing l.0 percent OWF Disperse Blue 27 0.5 percent OWF Sodium Acetate After dyeing the fabric was washed to remove any excess dyestuff. The design "CA was a full blue shade whereas the areas adjacent to it were stained a light shade of blue.

We claim:

1. The method for printing an indicia on a synthetic linear polyester sheet material comprising contacting a predetermined section of less than the total area of said material at an elevated temperature above 120 C. and below the shrink or decomposition temperature of said material with a member selected from the group consisting of a (a) substantially anhydrous halogenated aromatic hydrocarbon of the formula (Rama-XI,

wherein R and R are the same or different and each stands for a member selected from the group consisting of hydrogen, alkyl having one to four carbon atoms and alkenyl having two to four carbon atoms and R and R when attached to each other and to vicinal carbon atoms stands for a five to six membered ring, R is an alkylene having one to four carbon atoms or phenylene X is a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, n is a whole number from one to three, m is a whole number from one to two and (b) mixtures of said halogenated aromatic hydrocarbons; removing said member from said polyester, to provide an area having improved dyeability, and thereafter forming said indicia by applying a composition containing a tinctorially effective amount of a dispersed dyestuff for polyester sheet material to at least a portion of said area.

2. The method according to claim 1 wherein said polyester sheet material is contacted with said halogenated aromatic hydrocarbon in the liquid phase at a temperature from about l20 C. -200 C. for 10 to 20 seconds.

3. The method according to claim 2 where said halogenated aromatic hydrocarbon is a compound of the formula wherein X is chlorine or bromine and n is two or three.

4. The method according to claim 2 where said halogenated aromatic hydrocarbon is printed onto said polyester sheet material and thereafter said material is heated to -200 C.

5. The process according to claim 1 where said polyester is contacted with said aromatic hydrocarbon in the vapor phase at a temperature below the shrink or decomposition temperature of said polyester sheet material.

6. The process according to claim 5 wherein said polyester sheet material is treated with an aromatic hydrocarbon of the formula wherein X" is chlorine or bromine and n" is l or 2.

7. The process according to claim 1 wherein a portion of said polyester is initially treated with a resist agent which is insoluable in said halogenated aromatic hydrocarbon and thereafter the untreated portions are contacted with said halogenated aromatic hydrocarbon.

8. The process according to claim 1 wherein aid polyester sheet material is a film 0.5 to 20 mil thick.

9. The process according to claim l wherein said polyester sheet material is comprised of polyester fibers.

10. The polyester sheet material treated in accordance with the method of claim 1.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 644,080 Dated February 22, 1972 1 Robert W. McCullough, Vernon C. Smith, In n fl Frederick E; Barwick III and James B. Hobgood It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shownbelow:

Col. 3, line 62, change "1,2,5" to ---l,3,5---.

Col. 8, line 60, I change "Example 7" to ---Ex ample 9---.

Col. 8, line 61, change "Example 6" to ---Example 7--.

Col. 9, line 4, change "above" to ---below-'--.

Signed and sealed this 10th day of October 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer 1 Commissioner of Patents ORM PO 1050 (10 69) USCOMM-DC 60376-1 69 0 U.S. GOVERNMENT PRlNTING OFFICE: 1989 0-366334 

2. The method according to claim 1 wherein said polyester sheet material is contacted with said halogenated aromatic hydrocarbon in the liquid phase at a temperature from about 120* C. -200* C. for 10 4 to 20 seconds.
 3. The method according to claim 2 where said halogenated aromatic hydrocarbon is a compound of the formula wherein X'' is chlorine or bromine and n'' is two or three.
 4. The method according to claim 2 where said halogenated aromatic hydrocarbon is printed onto said polyester sheet material and thereafter said material is heated to 120*-200* C.
 5. The process according to claim 1 where said polyester is contacted with said aromatic hydrocarbon in the vapor phase at a temperature below the shrink or decomposition temperature of said polyester sheet material.
 6. The process according to claim 5 wherein said polyester sheet material is treated with an aromatic hydrocarbon of the formula wherein X'''' is chlorine or bromine and n'''' is 1 or
 2. 7. The process according to claim 1 wherein a portion of said polyester is initially treated with a resist agent which is insoluable in said halogenated aromatic hydrocarbon and thereafter the untreated portions are contacted with said halogenated aromatic hydrocarbon.
 8. The process according to claim 1 wherein aid polyester sheet material is a film 0.5 to 20 mil thick.
 9. The process according to claim 1 wherein said polyester sheet material is comprised of polyester fibers.
 10. The polyester sheet material treated in accordance with the method of claim
 1. 